The invention relates to self-lubricating abrasion resistant compositions useful for a wide range of applications. Particular utility is found in the dental and medical arts where such compositions are suitable for the formation and construction of dental prosthesis such as artificial teeth, inlays, onlays, and facings, crowns and bridges and artificial bone parts and medical prosthetic body parts, such as knee joints and/or other bone engaged surfaces and the like where abrasion resistance, polishability and aesthetics are important. Artificial teeth should exhibit certain physical and physicochemical characteristics to be suitable for use. They should be hard and resistant to chipping, durable, and stable to solvents, water, and heat. In addition, they should be of an aesthetically acceptable color, i.e., close to that of natural teeth, or be amenable to artificial coloration. The teeth should not cause excessive wear to opposing natural or artificial teeth, should not wear out of occlusion, and should be capable of being bonded firmly to supportive structures. They should also be amenable to ordinary means of physical shaping, grinding, and polishing, so as to minimize production costs.
Various metals and ceramics as used in the formation of prior art artificial teeth and other dental appliances possess certain inherent deficiencies which lessen their desirability in dental applications. Thus, the metallic color of gold, amalgam, and other metallic species serves as an aesthetic detraction to the wearer of appliances made therefrom. In addition, the high cost of most noble metals from which many such appliances are commonly made leads to a cost consideration whenever their use is contemplated. Ceramic materials, another common alternative, are often difficult to form into acceptable shapes, and may tend to be abrasive resulting in excessive wear upon contacting hard tissue, enamel and dentin. Such materials are also difficult to polish satisfactorily. These reasons together with factors related to cost, to consumer preference, to the technical skills of dental practitioners, and to convenience have motivated a search for alternative compositions suitable for the construction of dental appliances, inlays, onlays, crown and bridge material, artificial teeth and the like. Of the presently available organic compositions used for the construction of artificial teeth, most are composed of acrylics, often crosslinked by polyfunctional moieties.
As used herein xe2x80x9cself-lubricating materialxe2x80x9d means a material which is adapted to increase the lubricity of a product surface reduce friction, and consequently reduce wear.
As used herein xe2x80x9cwater insensitivexe2x80x9d means that water does not have a material effect upon the material so characterized.
It is to be understood that the term xe2x80x9cbisphenol-Axe2x80x9d is commonly utilized in the art to indicate the chemical compound 2,2-bis(4-hydroxyphenyl)propane. It is also to be understood that the term xe2x80x9cbis-GMAxe2x80x9d is commonly used to indicate the chemical compound 2,2-bis(4-(2-hydroxy-3-methacryloxypropoxy)-phenyl)propane, otherwise referred to as xe2x80x9cdigycidyl methacrylate ester of bisphenol-A.xe2x80x9d
Dentsply in U.S. Pat. Nos. 4,396,476, 4,396,377 and 4,698,373 (the disclosures of which are incorporated herein by reference) discloses interpenetrating network teeth, but does not disclose self-lubricating abrasion resistant compositions as required by the present invention.
Thornton U.S. Pat. No. 2,345,305 discloses making artificial teeth comprised of different plastic materials for the face (xe2x80x9cenamelxe2x80x9d) and body portions. Note FIG. 17, and page 4, column 2, lines 21-24. Another composite plastic tooth structure is disclosed by Cornell U.S. Pat. No. 3,488,846.
Rosenkranz et al. U.S. Pat. No. 3,928,299 discloses an organic homopolymer or random copolymer containing urethane groups.
Michl et al. in U.S. Pat. Nos. 4,267,097 and 4,281,991 (the disclosures of which are incorporated herein by reference) disclose artificial teeth prepared from (a) particle/bead PMMA, (b) a liquid monomer such as the adduct of hydroxymethacrylates and diisocyanates or difunctional esters of (meth)acrylic acids or mixtures thereof, and (c) micro-fine inorganic fillers. Michl et al do not disclose self-lubricating abrasion resistant hardenable compositions as required by Applicants"" invention.
Walkowiak et al. in U.S. Pat. Nos. 4,308,190 and 4,369,262 disclose dental paste materials of a polymerizable acrylic ester, a crosslinked bead polymer, and a particulate inorganic filler and do not disclose self-lubricating abrasion resistant hardenable compositions, or interpenetrating network compositions for making artificial teeth as required by Applicants"" invention.
Simpson in U.S. Pat. No. 4,361,676 discloses a sag-resistant, pumpable composition comprising a liquid material dispersed throughout a synthetic, continuous crosslinked polymer matrix.
Wright et al. in U.S. Pat. No. 4,598,111 disclose the use of various divinyl compounds, including divinyl dimethylsilane (column 6, line 35) as a crosslinking agent for (meth)-acrylate monomer systems. Other patents of this general type include, for example, Kohno et al. U.S. Pat. No. 4,761,436; dimethyldivinylsilane as a comonomer; column 3, line 29); Feinberg et al. U.S. Pat. No. 4,894,315; column 3, lines 37-38); Fryd et al. U.S. Pat. No. 4,956,252; column 5, lines 43-44); and Kafka et al. U.S. Pat. No. 4,970,037; column 9, lines 16-17).
Yamazaki et al. in U.S. Pat. No. 4,826,893 disclose a dental composition comprising (a) a siloxane polymer, (b) a monomer copolymerizable with the siloxane polymer, (c) a polymerization catalyst, e.g. benzoyl peroxide, and optionally, (d) a filler.
Laundry in U.S. Pat. No. 3,084,436 discloses soft dental materials manufactured from mixtures of methacrylate monomers. Monofunctional esters together with vinyl-acetate or vinyl stearate are crosslinked with polyfunctional esters of acrylic or methacrylic acid. The resulting product is disclosed as being three dimensionally crosslinked.
Graham et al. in U.S. Pat. No. 3,087,875 disclose preparation of graft copolymers. Alkyl methacrylate and analogous polymers are dissolved in monomers such as alkyl acrylates, alkyl thioacrylates, and N-vinyl lactams. The monomers are subsequently grafted to the preformed polymers via photochemical initiation.
Cornell in U.S. Pat. No. 3,427,274 discloses hardenable materials formed from a mixture of methyl methacrylate homopolymer and styrenebutadiene copolymer latex coated with methyl methacrylate polymer which may be incorporated in a methacrylate-crosslinking agent composition to form hardenable compositions.
Chang in U.S. Pat. No. 3,452,437 discloses a dental restorative material formed from the xe2x80x9cdiglycidyl methacrylate of bisphenol-Axe2x80x9d (bis-GMA) to which a quantity of methyl methacrylate may be added.
Bruckmann et al. in U.S. Pat. No. 3,468,977 disclose the formulation of dental compositions from a mixture of a polymer and a monomer. The preformed uncrosslinked polymer beads are allowed to swell with monomer which may contain a crosslinking agent. Acrylic materials may be used for both the monomer and the polymer.
Petner in U.S. Pat. No. 3,470,615, teaches the formulation of a material suitable for use in the construction of dental appliances. A mixture of an uncrosslinked homopolymer and crosslinked copolymer is dissolved in a liquid polyglycol dimethacrylate to form a suspension which may be brushed on a substratum and subsequently hardened by heat to build up layers of polymeric material. A similar teaching may be found in U.S. Pat. No. 3,471,596, also to Petner et al. A thick liquid is provided which is useful in the building up of dental crowns and the like. The difunctional monomer may contain various thickening agents including poly(methyl methacrylate). In some embodiments, the poly(methyl methacrylate) may be supplemented with additional polymer which may be partially crosslinked with allyl methacrylate.
Lee in U.S. Pat. No. 3,539,533 discloses a filling material including a monomer solution filled with inorganic particulate filler. The monomer solution may be a mixture of methacrylate monomers containing bisphenol-A dimethacrylate.
Taylor in U.S. Pat. No. 3,597,389 discloses polyfunctional methacrylate monomers, including xe2x80x9cbisphenol-A glycidyl dimethacrylatexe2x80x9d (bis-GMA), polymerized with an inorganic filler to yield dental compositions.
Waller in U.S. Pat. No. 3,629,187 discloses the use of the isocyanate or diisocyanate adducts of bisphenol-A type compounds. These adducts are employed together with various inorganic fillers and liquid monomers to form liquid or paste compositions which are polymerizable either thermally or photochemically.
Dougherty in U.S. Pat. No. 3,647,498 discloses dental compositions which are composed of liquid-solid mixtures. The solid phase is an acrylate or methacrylate polymer in bead form.
Logemann in U.S. Pat. No. 3,649,608 discloses dental compositions which comprise solid bead polymers or copolymers of methacrylate type materials.
Lee in U.S. Pat. No. 3,751,399 discloses compositions for dental use comprising aromatic and alicyclic polyacrylates which are mixed together with other polyacrylate compounds especially those containing bisphenol-A structures.
Sperling in U.S. Pat. No. 3,833,404 discloses elastomers, especially acrylates, urethanes, butadienes, natural rubbers, and polyvinyl alcohol, are formulated which possess interpenetrating polymeric network type structures. These materials are disclosed as being xe2x80x9chardxe2x80x9d, but are used as vibration and sound damping insulators.
Highgate in U.S. Pat. No. 3,961,379 discloses an article manufactured from a crosslinked polymer which is swollen with a monomer containing a crosslinking agent.
Temin in U.S. Pat. No. 4,197,234 discloses dental restorative composite compositions and filler therefor.
Engel in U.S. Pat. No. 4,288,221 discloses durable polishable direct filling material.
Jarby in U.S. Pat. No. 3,469,317 discloses material for filling cavities.
Crowell in U.S. Pat. No. 2,315,503 discloses art of molding composite resins.
Crowell in U.S. Pat. No. 2,403,172 discloses art of molding resins of vinyl type.
Van Beuren Joy in U.S. Pat. No. 3,532,502 discloses dentures, compositions, and methods
Michl et al in U.S. Pat. No. 4,281,991 discloses dental prostheses.
Bauman et al in U.S. Pat. No. 4,771,110 discloses polymeric materials having controlled physical properties and processes for obtaining these.
Muramoto et al in U.S. Pat. No. 4,829,127 discloses composite resin particles, its preparation and resinous composition for coating use containing the same.
Bauman in U.S. Pat. No. 4,880,879 discloses abrasion resistant composite material and process for making the same.
Podszun et al in U.S. Pat. No. 4,937,144 discloses dental fillers.
Lee in Australian Patent Specification 50,674 discloses dental adhesive composites.
Mark et al in Encyclopedia of Polymer Science and Technology 1967, Volume 6, pages 627-628 discloses alkoxy silane coupling agents for glass. Page in Silane coupling agents, discloses alkoxy silane compling agents.
None of the foregoing patents discloses the novel compositions and prostheses having matrix material bonded or adapted to form self-lubricating abrasion resistant material in accordance with the invention.
It is an object of the invention to provide abrasion resistant dental compositions especially useful as dental appliances, dentures and other prostheses, inlays, onlays, facings, crowns and bridges and the like.
It is the object of the invention to provide an abrasion resistant polymer composition comprising polymerizable vinyl silane or siloxane monomers useful as a dental prosthesis.
It is an object of the invention to provide a dental composition which can be polymerized to form an abrasion resistant prosthesis such as an artificial tooth comprising the addition of polymerizable vinyl silane or siloxane monomers.
It is the object of the invention to provide an abrasion resistant dental prosthesis such as an artificial tooth comprising polymerizable vinyl dialkyl silane or siloxane monomers.
It is an object of the invention to provide a dental composition comprising polymerizable vinyl silane or siloxane monomers which can be polymerized to form an abrasion resistant prostheses such as an artificial tooth.
It is an object of the invention to provide a dental composition comprising polymerizable dimethyl divinyl silane or siloxane monomers which can be polymerized to form an abrasion resistant prosthesis such as an artificial tooth comprising polymerizable dimethyl divinyl silane or siloxane monomers.
It is an object of the invention to provide an abrasion resistant dental composition that can be molded to form an artificial tooth comprised of copolymers of polymerizable dimethyl divinyl silane or siloxane monomers and acrylate or methacrylate monomers.
It is an object of the invention to provide an abrasion resistant dental composition that can be molded to form an artificial tooth comprised of copolymers of polymerizable dimethyl divinyl silane or siloxane monomers and acrylate or methacrylate monomers interpenetrating swellable crosslinked copolymers of esters of acrylic and/or methacrylic acid.
It is an object of the invention to provide a dental product, such as, a dental prosthesis, artificial tooth, inlay, onlay, facing, crown or bridge which is wear resistant across its entire cross section.
It is an object of the invention to provide compositions which are useful in the construction of artificial teeth and other dental appliances, which compositions lead to products having superior physical and aesthetic characteristics.
xe2x80x9cAmbient temperaturexe2x80x9d as used herein unless otherwise specified refers to a temperature of 23xc2x0 C.
Unless otherwise specified blends disclosed herein are formed by stirring at ambient temperature until a homogeneous solution is produced.